首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   71540篇
  免费   12516篇
  国内免费   7269篇
化学   49918篇
晶体学   657篇
力学   4661篇
综合类   310篇
数学   8187篇
物理学   27592篇
  2024年   170篇
  2023年   1539篇
  2022年   1896篇
  2021年   2562篇
  2020年   3067篇
  2019年   2844篇
  2018年   2473篇
  2017年   2266篇
  2016年   3455篇
  2015年   3310篇
  2014年   3957篇
  2013年   5146篇
  2012年   6582篇
  2011年   6727篇
  2010年   4469篇
  2009年   4251篇
  2008年   4596篇
  2007年   4112篇
  2006年   3761篇
  2005年   3135篇
  2004年   2428篇
  2003年   1922篇
  2002年   1751篇
  2001年   1471篇
  2000年   1355篇
  1999年   1533篇
  1998年   1304篇
  1997年   1291篇
  1996年   1289篇
  1995年   1051篇
  1994年   921篇
  1993年   763篇
  1992年   675篇
  1991年   580篇
  1990年   501篇
  1989年   386篇
  1988年   337篇
  1987年   274篇
  1986年   249篇
  1985年   204篇
  1984年   143篇
  1983年   102篇
  1982年   80篇
  1981年   67篇
  1980年   65篇
  1979年   32篇
  1978年   30篇
  1977年   40篇
  1976年   30篇
  1973年   28篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
A convenient direct transformation of p-nitrobenzyl 6-(1′-hydroxyethyl)-1-azabicyclo-(3.2.0)heptane-3,7-dione-2-carboxylate to N-formimidoyl thienamycin utilizing the silylated derivative of N-formimidoyl cysteamine is described.  相似文献   
982.
Direct trimethylsilylation1) of phenanthrene in different molar ratio of phenanthrene/sodium/trimethylchlorosilane is reported and discussed. Instead of the aromatic silyl compounds, such as 9-trimethylsilylphenanthrene (V), the hydroaromatic silyl compounds, such as 9, 10–bis (trimethylsilyl)-9, 10-dihydrophenanthrene (I) were obtained preferentially. Structure of these compounds are characterized and discussed. These silylated products have a general trend to change their properties during long time storage in the atmosphere under exposure to light. A significant difference of chemical shifts between silylated aromatic compound (V) and silylated hydroaromatic compound (I-IV) was observed.  相似文献   
983.
A rapid and sensitive method for the determination of 1-aminocyclopropane-1-carboxylic acid (ACC) in apple tissues has been described. This method is based on the derivatization of ACC with 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ), and separation and quantification of the resulting FQ-ACC derivative by capillary electrophoresis coupled to laser-induced fluorescence detection (CE-LIF). Our results indicated that ACC derivatized with FQ could be well separated from other interfering amino acids using 20 mM borate buffer (pH 9.35) containing 40 mM sodium dodecyl sulfate and 10 mM Brij 35. The linearity of ACC was determined in the range from 0.05 to 5 microM with a correlation of 0.9967. The concentration detection limit for ACC was 10 nM (signal-to-noise = 3). The sensitivity and selectivity of this described method allows the analysis of ACC in crude apple extracts without extra purification and enrichment procedure.  相似文献   
984.
甲烷二氧化碳介质阻挡放电转化产物分布研究   总被引:7,自引:0,他引:7  
针对介质阻挡放电甲烷二氧化碳转化实验,分析了反应的产物分布,探讨了进料组成和反应器结构对反应的影响.反应产物包括:高H2/CO摩尔比的合成气、气态烃、高辛烷值的汽油组分、醇和酸等含氧有机物.对所述电极结构,产物的选择性随碳数增加而降低;高的甲烷进料浓度有利于烃的生成,对醇和酸的最佳甲烷进料体积分数范围在67.4%~75.1%;放电间隙越小,原料转化率和烃、酸的选择性越大,大的放电间隙对醇的生成有利.  相似文献   
985.
流动注射在线共沉淀预富集火焰原子吸收法测定痕量铜   总被引:3,自引:0,他引:3  
研究了以Ni^2+-DDTC为共沉淀载体,流动注射在线共沉淀预富集-火焰原子吸收光谱法测定痕量铜的体系,在0.3mol.L^-1的硝酸介质中,铜离子在编织反应器中与Ni^2+-DDTC(产生共沉淀,并被收集在编织器内壁上,用甲基异丁基酮(MIBK)在线洗脱沉积物并引入火争原子化器中测定。当富集时间为40s时,40μg.L^-1的铜10次测定的相对标准偏差为3.0%,灵敏度提高60倍,检出限(3σ)  相似文献   
986.
Simmonds等报道异戊烯基化的查耳酮和黄烷酮对昆虫具有拒食活性[1],Echeverri等发现,从植物Passiflorafoetida树脂中分离到的4,7-二甲氧基莰非醇(1)在很低的浓度下(40μg/g)对昆虫Dionejuno的幼虫也具有...  相似文献   
987.
新颍Mo-Cu-Se簇合物{MoCu3Se3I}(PPh3)3O·0.5CH2Cl2是由[Et4N]2MoSe4、Cu(PPh3)2NO3和KI在乙腈和二氯甲烷1∶1的混合溶剂中反应所得。晶体属单斜晶系,空间群P21相似文献   
988.
The localized molecular orbitals and their energy levels for the clusters [Fe3S4(SH)3]2–, [(HS)3Fe3S4·Ni(PH3)]2–, [Mo3S4(OH2)9]4+, and [Mo3S4·Ni]4+ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe3S4]+ and [Mo3S4]4+ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M 3(3-S)(-S)3} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M3S3} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo3S4]4+ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe3S4]+ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo3S4]4+ cluster.  相似文献   
989.
A series of adamantanamine-(OCH2CH2)n-phenothiazine (n = 0, 1, 2, 3) electron donors was synthesized. Photoinduced electron transfer was observed in the supramolecular complex of the phenothiazine derivatives with p-nitrobenzoyl-β-cyclodextrin (NBCD) through binding of the adamantyl group by the NBCD cavity, which is stabilized clearly via hydrophobic interactions in aqueous solution. Detailed Stern–Volmer constants were measured and they were partitioned into dynamic Stern–Volmer quenching constants and static binding constants. The results revealed an efficient electron transfer process inside the supramolecular systems compared to that controlled by diffusion. This observation also indicates that the chain length will influence the electron transfer efficiency of a supramolecular donor–acceptor system.  相似文献   
990.
As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag+, respectively.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号